CN109817974B - Sodium ion nickel manganese magnesium iron quaternary positive electrode material and preparation method thereof - Google Patents

Sodium ion nickel manganese magnesium iron quaternary positive electrode material and preparation method thereof Download PDF

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CN109817974B
CN109817974B CN201910238583.4A CN201910238583A CN109817974B CN 109817974 B CN109817974 B CN 109817974B CN 201910238583 A CN201910238583 A CN 201910238583A CN 109817974 B CN109817974 B CN 109817974B
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翁俊迎
李爱香
周朋飞
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Shandong University of Technology
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Abstract

A sodium ion nickel manganese magnesium iron quaternary positive electrode material and a preparation method thereof belong to the technical field of sodium ion battery electrode materials, and are characterized in that: the chemical formula of the anode material is NaxNiyMnzMg0.9‑y‑zFe0.1O2Wherein x is more than or equal to 1 and more than or equal to 0.67, y is more than or equal to 0.5 and more than or equal to 0.2, and z is more than or equal to 0.7 and more than or equal to 0.3, adopting an electrostatic spinning technology to prepare a precursor material with a nanofiber structure with uniformly distributed sodium, nickel, cobalt, magnesium and iron, and sintering the precursor at a high temperature to obtain the P2/O3 composite structure Na of the porous nanofiberxNiyMnzMg0.9‑y‑zFe0.1O2And (3) a positive electrode material. The method has the advantages of simple operation, continuous batch production, high specific capacity of the product, good cycle performance and the like, and has very high economic value and wide application prospect.

Description

Sodium ion nickel manganese magnesium iron quaternary positive electrode material and preparation method thereof
Technical Field
A sodium ion nickel manganese magnesium iron quaternary positive electrode material and a preparation method thereof belong to the technical field of sodium ion battery electrode materials.
Background
With the development of renewable energy sources such as solar energy, wind energy, tidal energy and the like, a battery energy storage system with the characteristics of large scale, low cost, high safety and the like is urgently needed to be constructed so as to meet the storage and power generation grid connection of the future renewable energy sources. Although lithium ion batteries have already occupied the power market for portable electronic devices, they are increasingly being used as power sources for new electric vehicles. However, due to the limitation of the storage amount (about 0.006% of the storage amount of the crustal element) and distribution (about 70% in south america) of lithium element in the crustal, the development of lithium ion batteries in the field of large-scale energy storage is severely limited due to the increasing shortage of lithium resources and high cost. In recent years, sodium ion batteries have been increasingly researched and developed as chemical energy storage systems. Sodium belongs to a main group with lithium and has similar physical and chemical properties, so that sodium-ion batteries have similar working principle as lithium-ion batteries. Meanwhile, the reserves of the sodium element are more abundant (about 2.64 percent of the reserves of the crust element) and are uniformly distributed. Therefore, from the viewpoint of cost reduction and practical application, the development of sodium ion batteries for large-scale energy storage has great potential and important practical significance.
Currently, there is a great distance from the practical application of research and development of sodium ion batteries, mainly because the radius of sodium ions is large (0.12 a), which brings great challenges to the design of electrode materials, especially positive electrode materials that play a decisive role in the electrochemical performance of sodium ion batteries. Therefore, the development of positive electrode materials with high specific capacity, stable structure, high working voltage, low cost, good safety and other properties has become the focus of current research on sodium ion batteries. The research and development of the positive electrode material of the sodium-ion battery are mainly focused on the layered Na x MO2(M is Co, Ni, Mn, Fe, etc.) oxide, tunnel metal oxide, polyanion-type compound, prussian blue-type compound, etc. Wherein, the layer is Na x MO2The oxide system becomes a hot point of research because of adjustable electrochemical active elements and abundant systems. Delmas et al divide the layered oxide into structures O3, O2, P3, P2, etc., wherein: o and P each represent Na+O is an octahedron and P is a triangular prism; the numbers 2 and 3 represent the stacking of oxygen atoms, 2 being ABBAABBA … and 3 being ABCABC …. With Na+The content of ions in the alkali metal layer is increased, and the material is easier to generate sodium octahedral coordination; conversely, when the sodium ion content is small, the sodium prism coordination is more likely to be formed. Thus Na in comparison with O structure x MO2In other words, Na of P junction x MO2The sodium content of (a) is generally low. The structural characteristics of the layered oxide determine its electrochemical properties, and the phase structure is similar to that of the original stateSodium content, stability of the layer, environment around the sodium atoms, etc. Common layered close-packing patterns are O3 and P2 types. Among them, the O3 structure has a higher initial sodium content than the P2 structure, and thus has a higher capacity. However, the P2 structure oxide has larger interlayer spacing, and sodium ions diffuse therein with lower diffusion barrier, thereby showing higher ion conductivity.
However, layered Na x MO2Oxide materials still suffer from the following problems: (1) during the charging and discharging process, more phase transformation occurs to cause structural distortion or collapse, so that the cycling stability and the rate capability of the sodium ion battery are poor; (2) meanwhile, the material has poor stability in air, and is easy to generate side reaction with moisture and carbon dioxide, so that the storage cost is high; (3) no high-efficiency preparation process meets the requirements of macroscopic quantity and controllable preparation of the materials. Therefore, an effective strategy (phase structure regulation, element doping and micro-nano structure construction) is sought for improving the electrochemical performance and the structural stability and developing a macro-controllable preparation technology, namely layered Na x MO2The focus of the oxide system study.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art, and provides the sodium ion nickel manganese magnesium iron quaternary positive electrode material which has high structure stability, excellent electrochemical performance and simple preparation process, and the preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: the sodium ion nickel-manganese-magnesium-iron quaternary anode material is characterized in that: chemical formula is NaxNiyMnzMg0.9-y-zFe0.1O2Wherein x is more than or equal to 1 and more than or equal to 0.67, y is more than or equal to 0.5 and more than or equal to 0.2, and z is more than or equal to 0.7 and more than or equal to 0.3; the microstructure is a porous nanofiber morphology, and the phase structure is a P2/O3 composite layered structure.
The preparation method of the sodium ion nickel-manganese-magnesium-iron quaternary positive electrode material of claim 1 is characterized by comprising the following steps: the method comprises the following steps:
1) dissolving PAN and PMMA in N, N dimethyl formamide to obtain PAN-PMMA mucus, wherein the concentrations of PAN and PMMA in the PAN-PMMA mucus are both 0.03 g/mL-0.07 g/mL; then dissolving sodium salt, nickel salt, manganese salt, magnesium salt and ferric salt into the prepared PAN-PMMA mucus to prepare a spinning solution, wherein the total molar mass of metal ions in the spinning solution is 3-10 mmol;
2) pouring the spinning solution into an injector, and controlling the advancing speed of the spinning solution by using an injection pump; copper foil is adopted as a collector on a roller, positive high voltage is applied between a needle head and a receiving copper foil to excite spinning, and the copper foil is connected with negative high voltage to collect spinning; collecting white fiber films on the copper foil after continuous spinning;
3) fiber stabilization at low temperature converts thermoplastic PAN into a non-plastic ring or trapezoidal compound and PMMA melts; then heating to sintering temperature and preserving heat to complete NaxNiyMnzMg0.9-y-zFe0.1O2The PMMA is depolymerized, and PAN is decomposed, wherein the PMMA can be completely volatilized to form pores in the nano fibers; cooling to obtain final product NaxNiyMnzMg0.9-y-zFe0.1O2And (3) a positive electrode material.
The invention adopts the electrostatic spinning technology to prepare the precursor with uniform distribution of five elements of sodium, nickel, manganese, magnesium and iron and a nanofiber structure. Na of P2/O3 composite structure of porous nanofiber is obtained through high-temperature heat treatment processxNiyMnzMg0.9-y-zFe0.1O2And (3) a positive electrode material. The microstructure of the porous nanofiber is beneficial to rapid transmission of sodium ions, the P2/O3 composite phase structure can integrate the advantages of high stability of a P2 phase structure and high specific capacity of an O3 phase structure, and the structural change of the material in the charging and discharging process is relieved by the synergistic effect of four elements, namely Ni, Mn, Fe and Mg, so that the sodium ion battery anode material with high specific capacity, stable structure, long cycle life and low cost is prepared. The method has the advantages of simple operation, strong controllability of process conditions, contribution to realizing continuous batch production, high specific capacity, good cycle performance and the like of products, and very high economic value and wide application prospect.
Preferably, the concentration of PAN and PMMA in the PAN-PMMA mucus in the step 1) is 0.035 g/mL-0.05 g/mL, and the temperature of the PAN-PMMA mucus and the spinning solution is 40-70 ℃.
Preferably, the sodium salt, the nickel salt, the manganese salt, the magnesium salt and the iron salt in the step 1) are respectively one or a mixture of more than two of acetic acid, sulfate and nitrate containing corresponding metal ions; the total molar mass of the metal ions in the spinning solution is 5 mmol-7 mmol.
The fiber structure of the prepared material is more uniform and the yield is higher.
Preferably, the advancing speed of the spinning solution in the step 2) is 10 μ L min-1~30 μL min-1The positive high voltage applied between the needle head and the receiving copper foil is 12 kV-18 kV, and the negative high voltage applied between the copper foil and the receiving copper foil is-5 kV-0 kV.
Preferably, the distance between the copper foil and the needle head in the step 2) is 15 cm-20 cm, the rotating speed of the roller is 100-400 rpm/min, and the transverse moving range of the needle head is 3 cm-6 cm.
More preferably, the positive high voltage in the step 2) is 15kV to 17 kV, the negative high voltage is-4 kV to-2 kV, the distance between the copper foil and the needle is 18cm, the rotating speed of the roller is 250 rpm/min to 300 rpm/min, the transverse moving range of the needle is 5cm, and the obtained fiber membrane is larger in area and more uniform in thickness.
Preferably, the temperature for stabilizing the fibers at the low temperature in the step 3) is 200-300 ℃, the stabilizing time is 0.5-2 h, and the atmosphere is inert gas or air.
More preferably, the fiber is stabilized at the low temperature in the step 3) to obtain the fiber with the temperature of 230-280 ℃, the stabilizing time of 1-1.5 h and the atmosphere of inert gas.
Preferably, the heating rate of the heating to the sintering temperature in the step 3) is 1 ℃/min-5 ℃/min, the sintering temperature is 800 ℃ to 950 ℃, the heat preservation time is 15 h-20 h, and the atmosphere is inert gas, air or oxygen.
More preferably, the heating rate of the heating to the sintering temperature in the step 3) is 2 ℃/min-3 ℃/min, and the high-temperature sintering temperature is 850 ℃ to 900 ℃.
Preferably, the temperature reduction in the step 3) adopts liquid nitrogen quenching and speed-controlled temperature reduction of 5 ℃/min-1~20℃/min-1Or cooling along with the furnace.
Compared with the prior art, the invention has the beneficial effects that: the invention aims to solve the problem of layered Na of the existing sodium-ion battery x MO2The macro-controllable preparation and the rapid capacity attenuation of the anode material, and the like, and provides Na with a P2/O3 composite structure of porous nanofiberxNiyMnzMg0.9-y-zFe0.1O2A quaternary anode material and a preparation method thereof. The method is suitable for industrial production, and has the advantages of high automation program and stable product quality. The prepared quaternary positive electrode material has uniform element distribution and excellent electrochemistry and is beneficial to promoting the sodium ion battery to develop to practicality. Compared with the prior art, the porous nanofiber Na with the P2/O3 composite structurexNiyMnzMg0.9-y-zFe0.1O2The quaternary positive electrode material and the preparation method thereof have the beneficial effects that:
(1) prepared NaxNiyMnzMg0.9-y-zFe0.1O2The quaternary positive electrode material has the morphology of porous nanofibers and a P2/O3 composite phase structure, and has good structural stability and long cycle life when used as a positive electrode material of a sodium-ion battery.
(2) The preparation method has the advantages of simple process, adjustable and controllable parameters in production, low energy consumption and suitability for industrial mass and continuous production.
(3) The structural stability of the material can be obviously improved through the synergistic effect of the co-doping of a plurality of elements, the stability in the charging and discharging process is maintained, and Na with a P2/O3 composite structure is enabledxNiyMnzMg0.9-y-zFe0.1O2The characteristics of the quaternary positive electrode material are maintained, and the sodium ion positive electrode material prepared by the method has application prospects in the field of large-scale energy storage of secondary batteries.
Drawings
Fig. 1 is a scanning electron microscope image of a nanofiber precursor obtained in example 1 of the present invention.
FIG. 2 shows Na obtained in example 1 of the present invention0.8Ni0.3Mn0.5Mg0.1Fe0.1O2And (3) a scanning electron microscope image of the cathode material shows a porous nanofiber structure.
Fig. 3 is a scanning electron microscope image of the nanofiber precursor obtained in example 2 of the present invention, and it can be seen that the arrangement of nanofibers can be adjusted by increasing the rotation speed of the roller.
FIG. 4 shows Na obtained in example 1 of the present invention0.8Ni0.3Mn0.5Mg0.1Fe0.1O2The positive electrode material has an X-ray powder diffraction pattern, and the phase structure of the positive electrode material is a P2/O3 composite phase.
FIG. 5 shows NaNi obtained in example 1 of the present invention0.8Co0.1Al0.05Cu0.05O2After the cathode material is used as a cathode to assemble a CR2032 button sodium-ion battery, the cycling performance under the current density of 100 mA/g is tested.
Detailed Description
The invention is further illustrated by the following specific examples, of which example 1 is the best mode of practice.
Example 1
1) Preparing 30 ml mucus with concentration of PAN and PMMA of 0.035 g/ml and 0.05g/ml respectively at 50 deg.C, and using sodium, nickel, manganese, magnesium and iron acetate according to formula Na0.8Ni0.2Mn0.6Mg0.1Fe0.1O2Preparing spinning solution with total metal ions and total molar mass of 6 mmol;
2) preparing a nanofiber precursor by electrostatic spinning, pouring the prepared spinning solution into an injector, and adjusting the propelling speed to 15 mu L min-1The positive high voltage is 16 kV, the negative high voltage is-3 kV, the distance between the copper foil and the needle is 18cm, the rotating speed of the roller is 280 rpm/min, and the transverse movement range of the needle is 5 cm. Stopping spinning after 12 h, and taking down the precursor;
3) heat treatment at high temperature to obtain Na0.8Ni0.3Mn0.5Mg0.1Fe0.1O2And (3) preserving the temperature of the anode material in a muffle furnace at 250 ℃ for 1.2h for stabilizing pretreatment. After the temperature is reduced to the room temperature, the temperature is raised to 880 ℃ at the heating rate of 2.5 ℃/min, and the heat preservation time is 17 hours. After the heat preservation is finished, quenching by adopting liquid nitrogen to obtain a positive electrode material;
4) preparing electrode plates and assembling the sodium ion battery for testing.
Example 2
1) Preparing 30 ml mucus at 50 deg.C, wherein the concentration of PAN and PMMA is 0.04 g/ml and 0.04 g/ml respectively, and sodium, nickel, manganese, magnesium and iron acetate are used according to formula Na0.85Ni0.4Mn0.4Mg0.1Fe0.1O2Preparing a spinning solution with total metal ions and total molar mass of 5 mmol;
2) preparing a nanofiber precursor by electrostatic spinning, pouring the prepared spinning solution into an injector, and adjusting the propelling speed to 25 mu L min-1The positive high voltage is 15kV, the negative high voltage is-4 kV, the distance between the copper foil and the needle is 17 cm, the rotating speed of the roller is 300 rpm/min, and the transverse movement range of the needle is 4 cm. Stopping spinning after 12 h, and taking down the precursor;
3) heat treatment at high temperature to obtain Na0.85Ni0.4Mn0.4Mg0.1Fe0.1O2The anode material is subjected to stabilization pretreatment by heat preservation for 1 h at 230 ℃ in a nitrogen atmosphere of a tubular furnace. After the temperature is reduced to the room temperature, the temperature is increased to 900 ℃ in a muffle furnace at the heating rate of 3 ℃/min, and the heat preservation time is 15 h. After the heat preservation is finished, cooling along with the furnace to obtain a positive electrode material;
4) preparing electrode plates and assembling the sodium ion battery for testing.
Example 3
1) Preparing 30 ml mucus PAN and PMMA with concentration of 0.05g/ml and 0.035 g/ml respectively at 60 deg.C, using sodium, nickel, manganese, magnesium and iron acetate according to chemical formula NaNi0.4Mn0.4Mg0.1Fe0.1O2Preparing a spinning solution with total metal ions and total molar mass of 7 mmol;
2) preparing a nanofiber precursor by electrostatic spinning, pouring the prepared spinning solution into an injector, and adjusting the propelling speedThe concentration is 20 mu L min-1The positive high voltage is 17 kV, the negative high voltage is-2 kV, the distance between the copper foil and the needle is 19cm, the rotating speed of the roller is 250 rpm/min, and the transverse movement range of the needle is 5 cm. Stopping spinning after 12 h, and taking down the precursor;
3) high-temperature heat treatment to obtain NaNi0.4Mn0.4Mg0.1Fe0.1O2The anode material is firstly subjected to stabilization pretreatment by heat preservation for 1.5h at 280 ℃ in a nitrogen atmosphere of a tubular furnace. After the temperature is reduced to room temperature, the temperature is raised to 850 ℃ in a muffle furnace at the heating rate of 2 ℃/min, and the heat preservation time is 18 h. After the heat preservation is finished, cooling along with the furnace to obtain a positive electrode material;
4) preparing electrode plates and assembling the sodium ion battery for testing.
Example 4
1) Preparing 30 ml mucus with concentration of PAN and PMMA of 0.03 g/ml and 0.07g/ml respectively at 40 deg.C, and using sodium, nickel, manganese, magnesium and iron acetate according to formula Na0.75Ni0.3Mn0.5Mg0.1Fe0.1O2Preparing a spinning solution with the total molar mass of total metal ions being 3 mmol;
2) preparing a nanofiber precursor by electrostatic spinning, pouring the prepared spinning solution into an injector, and adjusting the propelling speed to be 30 mu L min-1The positive high voltage is 18 kV, the negative high voltage is 0 kV, the distance between the copper foil and the needle head is 15 cm, the rotating speed of the roller is 400 rpm/min, and the transverse movement range of the needle head is 6 cm. Stopping spinning after 12 h, and taking down the precursor;
3) heat treatment at high temperature to obtain Na0.78Ni0.2Mn0.6Mg0.1Fe0.1O2The anode material is firstly subjected to stabilization pretreatment by heat preservation for 2 hours at 200 ℃ in a nitrogen atmosphere of a tube furnace. After the temperature is reduced to room temperature, the temperature is raised to 950 ℃ in the oxygen atmosphere of the tube furnace at the temperature rise rate of 5 ℃/min, and the heat preservation time is 18 h. After the heat preservation is finished, cooling along with the furnace to obtain a positive electrode material;
4) preparing electrode plates and assembling the sodium ion battery for testing.
Example 5
1) At 70 ℃, 30 ml of the solution is preparedThe mucus of PAN and PMMA has concentration of 0.07g/ml and 0.03 g/ml respectively, and is prepared by using sodium, nickel, manganese, magnesium and iron acetate according to the chemical formula of Na0.67Ni0.2Mn0.6Mg0.1Fe0.1O2Preparing a spinning solution with total metal ions and total molar mass of 10 mmol;
2) preparing a nanofiber precursor by electrostatic spinning, pouring the prepared spinning solution into an injector, and adjusting the propelling speed to 10 mu L min-1The positive high voltage is 12 kV, the negative high voltage is-5 kV, the distance between the copper foil and the needle is 20cm, the rotating speed of the roller is 100 rpm/min, and the transverse movement range of the needle is 3 cm. Stopping spinning after 12 h, and taking down the precursor;
3) heat treatment at high temperature to obtain Na0.78Ni0.2Mn0.6Mg0.1Fe0.1O2The anode material is firstly subjected to stabilization pretreatment by heat preservation for 0.5 h at 300 ℃ in a nitrogen atmosphere of a tube furnace. After the temperature is reduced to room temperature, the temperature is raised to 800 ℃ in a muffle furnace at the heating rate of 1 ℃/min, and the heat preservation time is 20 h. Taking out and quenching the anode material when the temperature is reduced to 300 ℃ along with the furnace after the heat preservation is finished to obtain the anode material;
4) preparing electrode plates and assembling the sodium ion battery for testing.
Example 6
1) Preparing 30 ml mucus at 50 deg.C, wherein the concentration of PAN and PMMA is 0.04 g/ml and 0.04 g/ml respectively, and sodium, nickel, manganese, magnesium and iron acetate are used according to formula Na0.78Ni0.1Mn0.6Mg0.2Fe0.1O2Preparing spinning solution with total metal ions and total molar mass of 6 mmol;
2) preparing a nanofiber precursor by electrostatic spinning, pouring the prepared spinning solution into an injector, and adjusting the propelling speed to be 20 mu L min-1The positive high voltage is 17 kV, the negative high voltage is-2 kV, the distance between the copper foil and the needle is 16 cm, the rotating speed of the roller is 300 rpm/min, and the transverse movement range of the needle is 5 cm. Stopping spinning after 12 h, and taking down the precursor;
3) heat treatment at high temperature to obtain Na0.78Ni0.1Mn0.6Mg0.2Fe0.1O2Positive electrode materialThe material is firstly subjected to stabilization pretreatment by heat preservation for 1 h at 260 ℃ in a nitrogen atmosphere of a tube furnace. After the temperature is reduced to the room temperature, the temperature is increased to 900 ℃ in a muffle furnace at the heating rate of 2 ℃/min, and the heat preservation time is 20 h. After the heat preservation is finished, the temperature is reduced by 10 ℃/min at the controlled speed-1Taking out the anode material after quenching to 300 ℃ to obtain an anode material;
4) preparing electrode plates and assembling the sodium ion battery for testing.
Cell testing for each example: 20 mg of PVdF (binder) is weighed and put into a mortar, then NMP is added dropwise for grinding, after the two are mixed uniformly, 20 mg of carbon black (conductive agent) is added, then NMP is added for grinding, when the mixture is ground to a proper state, 160 mg of prepared anode material is added for grinding, and after the mixture is ground for 30 min, slurry is coated on aluminum foil. Placing into a vacuum oven with temperature of 80 deg.C for 12 hr. And rolling the dried electrode plate to prepare an original sheet with the diameter of 10mm, weighing the original sheet and calculating the mass of the active positive electrode material. A step of charging a battery in a glove box, wherein the battery charging step comprises the following steps: and placing the cathode shell at the bottommost part, adding a sodium sheet into the cathode shell, then placing the diaphragm on the sodium sheet, dropwise adding electrolyte, then placing the electrode sheet, placing the active substance downwards, adding the stainless steel gasket, the elastic sheet and the anode shell, and finally packaging to form the button cell. And (4) performing constant current discharge on a blue test system to test the electrical performance.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.

Claims (6)

1. A sodium ion nickel manganese magnesium iron quaternary anode material is characterized in that: chemical formula is NaxNiyMnzMg0.9-y- zFe0.1O2Wherein x is more than or equal to 1 and more than or equal to 0.67, y is more than or equal to 0.5 and more than or equal to 0.2, and 0Z is more than or equal to 7 and more than or equal to 0.3; the microstructure is a porous nanofiber morphology, and the phase structure is a P2/O3 composite layered structure;
the preparation method comprises the following steps:
1) dissolving PAN and PMMA in N, N dimethyl formamide to obtain PAN-PMMA mucus, wherein the concentrations of PAN and PMMA in the PAN-PMMA mucus are both 0.03 g/mL-0.07 g/mL; then dissolving sodium salt, nickel salt, manganese salt, magnesium salt and ferric salt into the prepared PAN-PMMA mucus to prepare a spinning solution, wherein the total molar mass of metal ions in the spinning solution is 3-10 mmol;
2) pouring the spinning solution into an injector, and controlling the advancing speed of the spinning solution by using an injection pump; copper foil is adopted as a collector on a roller, positive high voltage is applied between a needle head and a receiving copper foil to excite spinning, and the copper foil is connected with negative high voltage to collect spinning; collecting white fiber films on the copper foil after continuous spinning;
3) fiber stabilization at low temperature converts thermoplastic PAN into a non-plastic ring or trapezoidal compound and PMMA melts; then heating to sintering temperature and preserving heat to complete NaxNiyMnzMg0.9-y-zFe0.1O2The PMMA is depolymerized, and PAN is decomposed, wherein the PMMA can be completely volatilized to form pores in the nano fibers; cooling to obtain final product NaxNiyMnzMg0.9-y- zFe0.1O2A positive electrode material;
the heating rate is 1-5 ℃/min when the temperature is raised to the sintering temperature, the sintering temperature is 800-950 ℃, the heat preservation time is 15-20 h, and the atmosphere is inert gas, air or oxygen;
and liquid nitrogen quenching is adopted for cooling.
2. The quaternary positive electrode material of sodium ion nickel manganese magnesium iron as claimed in claim 1, characterized in that: the concentration of PAN and PMMA in the PAN-PMMA mucus in the step 1) is 0.035 g/mL-0.05 g/mL, and the temperature of the PAN-PMMA mucus and the spinning solution is 40 ℃ to 70 ℃.
3. The quaternary positive electrode material of sodium ion nickel manganese magnesium iron as claimed in claim 1, characterized in that: the sodium salt, the nickel salt, the manganese salt, the magnesium salt and the ferric salt in the step 1) are respectively one or a mixture of more than two of acetate, sulfate and nitrate containing corresponding metal ions; the total molar mass of the metal ions in the spinning solution is 5 mmol-7 mmol.
4. The quaternary positive electrode material of sodium ion nickel manganese magnesium iron as claimed in claim 1, characterized in that: the advancing speed of the spinning solution in the step 2) is 10 mu L min-1~30 μL min-1The positive high voltage applied between the needle head and the receiving copper foil is 12 kV-18 kV, and the negative high voltage applied between the copper foil and the receiving copper foil is-5 kV-0 kV.
5. The quaternary positive electrode material of sodium ion nickel manganese magnesium iron as claimed in claim 1, characterized in that: in the step 2), the distance between the copper foil and the needle head is 15 cm-20 cm, the rotating speed of the roller is 100-400 rpm/min, and the transverse moving range of the needle head is 3 cm-6 cm.
6. The quaternary positive electrode material of sodium ion nickel manganese magnesium iron as claimed in claim 1, characterized in that: the temperature for stabilizing the fibers at the low temperature in the step 3) is 200-300 ℃, the stabilizing time is 0.5-2 h, and the atmosphere is inert gas or air.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102074683A (en) * 2010-12-10 2011-05-25 江南大学 Porous carbon nanofiber anode material for lithium ion battery and preparation method thereof
CN102362377A (en) * 2009-03-23 2012-02-22 住友化学株式会社 Lithium composite metal oxide and positive electrode active material
CN105210218A (en) * 2013-02-27 2015-12-30 尤米科尔公司 Doped sodium manganese oxide cathode material for sodium ion batteries
CN107437620A (en) * 2017-07-19 2017-12-05 广东迈纳科技有限公司 The preparation method of nickelic ternary NCM622 nano-materials
CN108574089A (en) * 2018-03-01 2018-09-25 上海电力学院 A kind of preparation method of hollow tubular lithium-rich manganese-based anode material
CN108767222A (en) * 2018-05-25 2018-11-06 厦门大学 A kind of preparation method of cation doping tertiary cathode material nanofiber
CN108987711A (en) * 2018-07-19 2018-12-11 中南大学 A kind of spherical shape sodium-ion battery anode quaternary material and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102362377A (en) * 2009-03-23 2012-02-22 住友化学株式会社 Lithium composite metal oxide and positive electrode active material
CN102074683A (en) * 2010-12-10 2011-05-25 江南大学 Porous carbon nanofiber anode material for lithium ion battery and preparation method thereof
CN105210218A (en) * 2013-02-27 2015-12-30 尤米科尔公司 Doped sodium manganese oxide cathode material for sodium ion batteries
CN107437620A (en) * 2017-07-19 2017-12-05 广东迈纳科技有限公司 The preparation method of nickelic ternary NCM622 nano-materials
CN108574089A (en) * 2018-03-01 2018-09-25 上海电力学院 A kind of preparation method of hollow tubular lithium-rich manganese-based anode material
CN108767222A (en) * 2018-05-25 2018-11-06 厦门大学 A kind of preparation method of cation doping tertiary cathode material nanofiber
CN108987711A (en) * 2018-07-19 2018-12-11 中南大学 A kind of spherical shape sodium-ion battery anode quaternary material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Layered Na-Ion Cathodes with Outstanding Performance Resulting from the Synergetic Effect of Mixed P- and O-Type Phases;Keller Marlou et al;《ADVANCED ENERGY MATERIALS》;20160204;第6卷(第3期);第1-11页 *

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